Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B43/00—Preparation of azo dyes from other azo compounds
  • C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
  • C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
  • C09B43/16—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents linking amino-azo or cyanuric acid residues
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
  • C09B62/043—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring containing two or more triazine rings linked together by a non-chromophoric link
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/02—After-treatment
  • D06P5/04—After-treatment with organic compounds
  • D06P5/08—After-treatment with organic compounds macromolecular

Definitions

• This invention relates to a process for dyeing or printing hydroxy group- or nitrogen-containing organic substrates employing disazo direct dyes and after-treating the dyed or printed substrate with a cationic fixing agent; furthermore, it relates to the novel disazo compounds employed therein and to a process for their production.
• the present invention provides a process for dyeing or printing hydroxy group- or nitrogen-containing organic substrates employing a compound which, in free acid form, corresponds to formula I, ##STR2## in which
• each R 1 independently, is hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy or --NHCOC 1-4 alkyl,
• each R 2 independently, is hydrogen, halogen, C 1-4 alkyl or C 1-4 alkoxy,
• each R 3 independently, is halogen, OH, C 1-4 alkoxy, --NHOH, NH 2 , an aliphatic, aromatic or cycloaliphatic amine radical or a saturated heterocyclic amine radical in which the nitrogen atom is part of the heterocycle which optionally contains further hetero atoms, and
• B is a divalent aliphatic or aromatic radical, with the proviso that each aromatic C 6 ring is bound in the 1,4-positions, or
• Dyeing and printing may be carried out in accordance with known methods.
• Preferred compounds of formula I to be employed are those in which B is an aromatic bridging member linked through the 1,4-positions of the aromatic C 6 -ring(s), which bridging member is free from sulphonic acid groups, or B, together with the NH-radicals to which it is bound, forms a piperazine ring.
• Y 1 is --CO--, --NHCO--, --NHCONH--, --(CH 2 ) 1-4 --, --NH--, --N ⁇ N--, --NHCOCONH--, --NHCOCH ⁇ CHCONH--, --OCH 2 CH 2 O--, --NHCOCH 2 CH 2 CONH-- or ##STR5## or
• the present invention provides the novel compounds of formula Ia and mixtures thereof, which compounds are in free acid or salt form, with the proviso that when both radicals R 1 are identical and are methyl or --NHCOCH 3 , each R 2 is hydrogen and B 1 is 1,4-phenylene, at least one of the radicals R 3 is other than chlorine.
• Any halogen is preferably fluorine, chlorine or bromine, more preferably it is fluorine or chlorine, especially chlorine.
• radicals R 1 and R 2 may be the same or different; preferably, they are identical.
• Any alkyl as R 1 and R 2 is preferably C 1-2 alkyl, more preferably methyl; any alkoxy, independently, is preferably methoxy or ethoxy, especially methoxy.
• R 1 is a --NHCOalkyl group, it preferably contains a C 1-2 alkyl group; especially, R 1 is --NHCOCH 3 .
• R 1 is preferably R 1a , where R 1a is hydrogen, chlorine, C 1-2 alkyl, C 1-2 alkoxy or --NHCOC 1-2 alkyl; more preferably, R 1 is R 1b , where R 1b is hydrogen, methyl, methoxy or --NHCOCH 3 ; even more preferably, R 1 is R 1c , where R 1c is hydrogen, methoxy or --NHCOCH 3 ; most preferably, R 1 is --NHCOCH 3 .
• R 2 is preferably R 2a , where R 2a is hydrogen, C 1-2 alkyl or C 1-2 alkoxy; more preferably, R 2 is R 2b , where R 2b is hydrogen, methyl or methoxy; most preferably, R 2 is hydrogen.
• Any alkoxy as R 3 is preferably methoxy.
• R 3 is an aliphatic amino group it is preferably a monoalkyl- or dialkyl-amino group in which the alkyl group contains 1 to 4 carbon atoms and is straight chain or branched and is optionally substituted by --NH 2 or by one or two hydroxy groups.
• Any aromatic amine radical as R 3 is preferably phenylamino in which the phenyl ring is optionally substituted by 1 or 2 substituents selected from halogen, C 1-4 alkyl, C 1-4 alkoxy and --NHCOC 1-4 alkyl.
• Any cycloaliphatic amine radical is preferably a C 5-6 cycloalkylamino group, especially a cyclohexylamino group.
• Any heterocyclic amine radical is preferably a morpholine, piperidine, piperazine or pyrrolidine group.
• R 3 is preferably R 3a , where R 3a is fluorine, chlorine, --OH, OCH 3 , --NH 2 , --NHOH, C 1-4 alkylamino, C 2-4 hydroxyalkylamino, N--C 1-4 --alkyl--N--C 2-4 hydroxyalkylamino, bis(C 2-4 hydroxyalkyl)amino, C 3-4 dihydroxyalkylamino, C 2-4 aminoalkylamino; phenylamino in which the phenyl ring is optionally substituted by 1 or 2 substituents selected from chlorine, methyl, methoxy and --NHCOCH 3 ; or morpholino; more preferably, R 3 is R 3b , where R 3b is fluorine, chlorine, NH 2 , C 1-2 alkylamino, C 2-4 hydroxyalkylamino, N--C 1-2 alkyl--N--C 2-4 hydroxyalkylamino, bis(C 3-4 hydroxyalkyl
• any hydroxy or amino substituent on an alkyl group is in other than the 1-position and when an alkyl group contains two hydroxy substituents, they are on different carbon atoms and the alkyl moiety contains 3 or 4 carbon atoms.
• Y 1 is preferably Y 1a , where Y 1a is --NHCO--, --NHCONH-- or --(CH 2 ) 1-4 --; especially, Y 1 is --NHCONH--.
• B 1 is preferably B 1a , where B 1a is 1,4-phenylene, ##STR7## or, together with the NH - radicals to which it is bound, forms a piperazine ring; more preferably, B 1 is B 1b , where B 1b is 1,4-phenylene, ##STR8## or, together with the NH - radicals to which it is bound, forms a piperazine ring; even more preferably, B 1 is B 1c , where B 1c is 1,4-phenylene or, together with the NH - radicals to which it is bound, forms a piperazine ring; most preferably, B 1 together with the NH - radicals forms a piperazine ring.
• Preferred compounds of formula Ia are those which, in free acid form, correspond to formula Ib, ##STR9## wherein R 1b , R 2b , R 3b and B 1 are as defined above; and wherein the radicals R 1b and R 2b , respectively, are identical and the radicals R 3b may be the same or different; for the compounds of formula Ib the same provisos as for the compounds of formula Ia are pertinent.
• radicals R 3b independently, are R 3c ;
• the cation of sulpho groups is not critical and may be any of those non-chromophoric cations conventional in the field of anionic direct dyestuffs.
• examples of such cations are alkali metal cations and unsubstituted and substituted ammonium cations e.g., lithium, sodium, potassium, ammonium, mono-, di- tri- and tetra-methylammonium, triethylammonium and mono-, di- and tri-ethanolammonium.
• the preferred cations are the alkali metal cations and ammonium, with sodium being the most preferred.
• the cations of the sulpho groups present may be the same or different and are preferably the same.
• the compounds also may be in a mixed free acid/salt form, where some of the sulpho groups are in free acid and some are in salt form.
• the present invention further provides a process for the preparation of compounds of formulae Ia and I, respectively, comprising reacting a compound which, in free acid form, corresponds to formula II, ##STR10## wherein Hal is halogen,
• each triazine radical by reacting with the corresponding amount of a base or a compound R 3x H, wherein R 3x has one of the significances of R 3 with the exception of OH and halogen.
• reaction of a compound of formula II with a compound of formula IIIa or III, respectively is carried out in accordance with known methods.
• the reaction is carried out at temperatures from 10° to 50° C.
• the replacement of the halogen atom by another group R 3 may be effected in accordance with conventional methods, preferably at pH 7 to 10 and at temperatures from 70° to 100° C.
• To prepare mixtures of compounds of formula I with respect to the radicals R 3 for example one equivalent of a compound of formula I is reacted with 0.01 to 1.5 equivalents of an amine, a base, an alcohol or ammonia.
• the compounds of formulae Ia and I, respectively, may be isolated in accordance with known methods, for example by salting out with a small amount of an alkali metal salt, filtering and drying in vacuo.
• the starting materials of formula II are either known or may be prepared in conventional manner by reacting the corresponding amino-monazo compound with cyanuric halide.
• the diamines of formula III and also the compounds R 3x H are either known or may be prepared in accordance with known methods from available starting materials.
• the compounds of formula Ia and mixtures thereof which are preferably in salt form are useful for dyeing or printing hydroxy group- or nitrogen-containing organic substrates.
• Preferred substrates are paper, leather and textiles comprising or consisting of cellulose fibres, such as cotton.
• the compounds according to the invention show high affinity for the substrate and therefore are good direct dyes.
• Dyeing and printing with the dyes of the invention may be carried out in accordance with known methods.
• Dyeing of natural regenerated cellulose such as cotton is preferably carried out according to the conventional exhaust dyeing method using temperatures from 40° to 100° C. Further suitable is the continuous dyeing method and thus processes such as cold pad-batch, pad-steam, pad-roll or pad-dry may be applied.
• the dyestuffs of the invention give deep dyeings and show high exhaustion yields. Furthermore, they are not adversely affected by electrolytes.
• the dyestuffs are also suitable for dyeing in combination with analogous dyes showing similar dyeing properties.
• Dyeings and prints on the above-mentioned substrates exhibit good wet fastnesses (such as fastness to washing or sweat) and good light fastness. Furthermore, they show good fastness to peroxide, perborate and chlorine.
• the wet-fastness properties of the direct dyestuffs on cellulose fibres containing textile material may be notably improved by the initially mentioned special resin after-treatment with selected auxiliaries. Particularly, this treatment gives improved wash-fastness properties, allowing repeated washing at high temperatures.
• Coupling is effected by adding the thus prepared diazo suspension dropwise within 40-50 minutes to 112.5 parts 3-aminoacetanilide (ca. 40%) which were dissolved in 150 parts water of 30°-35° by the addition of 85 parts 20% sodium carbonate solution at pH 6.5-7.0 and subsequent addition of 100 parts ice. While adding, the temperature is kept between -2° and 1° by the portionwise addition of further 500 parts ice and the pH is maintained at 6.6-7.0 by simultaneously adding 160 parts of 20% sodium carbonate solution. At the end of the diazo addition the thus obtained dyestuff precipitates. After 2 hours further stirring coupling is completed.
• condensation product of amino-monoazo dyestuff and cyanuric chloride is prepared starting with 0.5 instead of 0.3 moles 2-aminonaphthalene-4,8-disulphonic acid and using the corresponding increased amounts for the other reactants.
• Example 3 According to the method described in Example 3 but using a molar deficit (0.5 parts) of monoethanolamine instead of the ten-fold excess for the reaction with 18.9 parts of the dyestuff of Example 2, a mixture of dyes is obtained containing the dyestuffs of Examples 2 and 3 and additionally, the dyestuff which, in the free acid form, corresponds to formula, ##STR14## thus representing a direct dye mixture well suitable for dyeing of cotton resulting in a yellow shade.
• Dyeing is continued for 1 hour at 98°. During dyeing, the water that evaporates is continuously replaced. The dyed fabric is then removed from the liquor, rinsed with cold and hot water, soaped at the boil for 20 minutes in 500 parts water and 0.5 parts sodium alkylsulphonate, rinsed again and dried. A yellow dyeing having good light and wet fastnesses is obtained.
• the fabric is then shock-dried on a tension frame at 175°-180° in such a way that the cross-linking time of the dry fabric is 30-45 seconds at this temperature.
• the fixing agent is a reaction product (at 70° for 3 hours) of
• (C) 457 parts of a 50% solution of dimethyloldihydroxyethylene urea heated to 70°, to which 23 parts dicyandiamide as stabilizing agent are added.
• This product may be used as such or together with a catalyst for the cross-linking, e.g. magnesium chloride.
• the obtained yellow cotton dyeing fixed in such a way exhibits excellent wash-fastness and withstands repeated 60° washes and even a wash at the boil. At the same time a clear improvement of crease resistance is obtained, and the swelling value of the cellulose fibres is reduced.
• dyestuffs may be prepared which may be used according to the invention.
• These dyes in free acid form, correspond to the formula ##STR15## and are listed in the following Table 1. They dye cotton in a yellow shade, the dyeings obtained may be after-treated according to the method described in Application Examples C and D yielding in dyeings with notably improved wet-fastnesses.
• dyestuffs applicable according to the invention may be prepared in accordance with the method described in Examples 1-3. They correspond, in free acid form, to the formulae ##STR20## and are listed in the following Tables 2 and 3. With these dyestuffs cotton may be dyed in accordance with the dyeing method given in Application Examples A and B yielding yellow dyeings which exhibit good fastness properties. These fastness properties may be improved by after-treating the obtained dyeings according to the method of Application Examples C and D.
• the dyestuffs of Examples 1 to 75 are obtained in sodium salt form. They may, depending on the reaction/isolation conditions or by reacting the sodium salts in accordance with known methods, also be obtained in free acid form or in other salt forms, for example those salt forms indicated in the description hereinbefore.
• the halogen atom may be replaced partially by an amine radical depending on the amount of amine used.
• Direct dye mixtures are obtained which, depending on the amount and type of amine used for replacement, may show improved water solubility in connection with high affinity for the substrate.

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• 1982
  • 1982-12-06 FR FR8220528A patent/FR2518106B1/fr not_active Expired
  • 1982-12-06 CH CH707882A patent/CH669305GA3/de unknown
  • 1982-12-07 GB GB08234817A patent/GB2111538B/en not_active Expired
  • 1982-12-10 ZA ZA829100A patent/ZA829100B/xx unknown
  • 1982-12-10 BR BR8207197A patent/BR8207197A/pt unknown
  • 1982-12-10 IT IT49659/82A patent/IT1189436B/it active
  • 1982-12-10 JP JP57215679A patent/JPS58104957A/ja active Granted
  • 1982-12-10 ES ES518092A patent/ES518092A0/es active Granted
• 1984
  • 1984-05-02 US US06/606,341 patent/US4866163A/en not_active Expired - Lifetime
• 1986
  • 1986-03-13 BE BE1/011455A patent/BE904412Q/fr not_active IP Right Cessation
  • 1986-08-14 HK HK598/86A patent/HK59886A/xx not_active IP Right Cessation
  • 1986-12-30 MY MY695/86A patent/MY8600695A/xx unknown

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